Brooks



Feb. 14, 1956 L. BRooKs GRAPHITE PURIF'ICATION Filed Nov. 16. 1949 ELECTRGDE Iaco Zoo

TIME, HRS.

IN VEN TOR.

y1? rz .Brooks BY Wam/M4# AT T ORNEY United States Patent '50 GRAPHITE PURIFICATION Lynn Brooks, Bay City, Mich., assignor to United Carbon Products Co., Inc., Bay City, Mich.

Application November 16, 1949, Serial No. 127,594 8 Claims. (Cl. 22a-209.9)

This invention relates to a method of removing impurities from graphite and more particularly to a method for removing impurities from graphite articles as volatile reaction products.

This application is a continuation-impart of application No. 750,599, tiled May 26, 1947.

Many attempts have been made in the past to purify graphite. These methods were successful in so far as they produced a graphite of sufficient purity to satisfy the requirements then established.

However, certain of todays arts require a graphite f a purity never contemplated in the past. In the arc spectograph, for example, analyses are carried out for the detection of impurities present in amounts as low as a few hundredths of a part per million. The graphite electrodes used as the arc source in such an analysis must be of a correspondingly high purity as not to mask the spectrum of the sample. Another use today of high purity graphite is in nuclear reactors wherein it is used as a neutron moderating agent. Since certain elements display an avid ability to capture, i. e., to absorb neutrons, thereby reducing the number available for sustenance of the chain reaction, it is desirable that the graphite be exceptionally free of such substances. It has not been found possible to obtain a graphite of suicient purity for these purposes by the prior processes due to certain inherent faults in these processes.

This invention has as an object a method of obtaining graphite of high purity. A further object is a method for treating graphite articles to remove impurities therefrom without structural damage to the article. Other objects will appear hereinafter.

Broadly these objects are accomplished by first subjecting the graphite to be purified at an elevated temperature to the action of a chlorinating agent thus removing certainimpurities as volatile chlorides and subsequent to this treatment subjecting the graphite at a more elevated temperature to the action of a iluorinating agent, which causes further purification by removing certain impurities as volatile fluorides. v

The invention is more fully described in the description of the process below and the accompanying figures, of which:

Figure l is a semi-diagrammatic view in sectional elevation of a suitable apparatus for carrying out the process of this invention; and

Figure 2 is a graphic outline of the process.

Figure l represents an arrangement for carrying out the process of the invention in a granular carbon resistance type furnace. The steel shell 1 of the furnace is lined with fire brick 2. The graphite articles 3 to be purified are placed in a pure petroleum coke bed 4 and are spaced evenly between the graphite furnace electrodes 5, 6 which extend through the walls of the furnace. The electrodes are connected through leads 7, 8 to a suitable source of current represented here by transformer 9. Porous tubes 10 of a suitable material, such as graphite are 2,734,800 Patented Feb. 14, 1956 mounted in the coke bed 4 beneath graphite articles 3 for the purpose of introducing the reactants to the graphite articles. The reactants are introduced to the furnace and distributed to porous tubes 10 by means of header pipe 11. Hood 12 and duct 13 serve toremove the gaseous reaction products and excess reactants. Heating of the furnace is accomplished by the resistance of the graphite articles 3 and the coke bed 4 to an electric current applied between electrodes 5, 6. The distribution of the heating within the furnace and the temperature are controlled by selection of the size of the particles of the coke bed 4 and the amount of current applied to the electrodes 5, 6.

The temperature of the furnace may be determined by the usual thermocouple or optical pyrometer methods. It is to be understood that the furnace described above is only by way of example and that the process of the present invention can be carried out in other types of furnaces.

The following example of the practice of the present invention was carried out in a furnace such as described above. 874 lbs. of impure'graphite in the form of thirty bars each 261/2 x 4% x 4% made up the charge. These bars were of synthetic graphite having a specific gravity of about 1.65 prepared by graphitizing bars of petroleum coke powder bonded with coal tar pitch. These bars were loaded in a graphite resistor furnace in the manner taught above. The procedure from this point is graphically outlined in Figure 2. The heating of the furnace was started by applying current to the furnace electrodes. As can be seen from Figure 2 when the temperature of the furnace is approximately 950 C. CC14 vapor carried in nitrogen gas was passed into the furnace. The introduction of CCL; by means of header pipe 11 and porous tubes 10, was continued at an even rate until the charge attained a temperature of 1950 C. This took 21/2 hours during which period a total of 63 lbs. of CCl4 carried in 100 cu. ft. of nitrogen gas was passed into the furnace. When the temperature of the charge reached 1950 C. the introduction of CCl4 was stopped and the introduction of diiluoro-dichloromethane, Freon-lZ, was started through header pipe 11 and porous tubes 10. Heating was continued for a period of six and one-half hours until the charge temperature reached approximately 2500 C. The Freon-IZY was introduced at a steady rate during this period, the total amount being 61 lbs. At this point the heating was stopped, the Frech-12 replaced with nitrogen gas, and the furnace allowed to cool.

An analysis of the impure graphite introduced to the furnace indicated a total ash content of 600 parts perv million and an initial boron content of 0.60 part per million. By employing the process described above, the ash content was reduced to approximately 10 parts per million and the boron content was reduced to 0.02 part per million.

In place of the CLl4 chlorine gas may be used or any fully chlorinated hydrocarbon, such as hexachloropropylene which will dissociate to give free chlorine at a temperature below about 900 C. may be used.

v As alternative uorinating agents C21-74, CF4 and other fully halogenated hydrocarbons containing uorine which dissociate to release free fluorine at a temperaturebelow about l800 C. are also satisfactory. Fluorine itself or HF may also be used but are undesirable in view of their corrosive effect upon the apparatus.

It has been found desirable to continue the chlorination until the graphite has attained a temperature of about l860 C. It was found that it' the chlorination was not continued to this temperature that certain contaminants, such as, calcium and magnesium were not completely removed as their chlorides. Since their iluorides are less volatile, it was found difficult to remove those portions remaining during the uorination step. If the chlorination was continued to a temperature of about 1860" C., it was found that this difficulty was obviated since these impurities were apparently substantially completely removed during the chlorination step. Though the fiuorination might be started at a: lower temperature than the i860 C. attained during.y thev chlorination step, it has been found desirable to maintain that temperature while replacing the chlorinating. agent With the uorinat ing agent and continue heating the graphite to. a higher temperature. This is so for two reasons. First, higher temperatures aid in the removal of. those impurities removed as fluoridesg. and, second,` the higher temperatures, that is, greater than 1860o C., obviate the possibility of the graphite articles eroding andY disintegrating. Carbonl reacts rather vigorously with uorine aty ordinary temperatures to form volatile products; at higher temperatures, however, these products dissociate. Therefore,v if. the fluorinating agent is not introduced except above the dissociation temperature of. the carbon and uorine reactionproductanoy reactionof the fiuorine-with the graphite will occur. It is convenient from the standpoint. of operating procedure. tol merely replace the chlorinating agentwithY thehuorinating agent` when the'. ternperature of 1860? C. is attained.. and continueA the heatingfrom that point, butv further no erosionof the graphite articles was observedV vv-hen'` theM process was carried out inthismanner.. Thus theprocessfof. the. invention affords a means for treating graphite articles toy removeV impurities therefrom without destroying the conformation: of the articles.

The fiuorination step. wasfound absolutely necessary to attain4 the removal of boron. Severalattempts were made toV use chlorinating agents alone up.l to temperatures even greater than 2800" C. in none of theseattempts was it foundpossible: to. lower thev boron content. to even as low as.0.10 part per million.

Though uorination temperatures as low as 2100."`C. orv 2200 C. resultedin substantial removal oflthe boron, it wasfound desirable to-heat the. graphite to a temperature ofabout 24005 C'. or higher while the uorinating agent wasintroduced.

Sweeping` the.A furnace. during. the cooling period with nitrogen or. helium wasfound. to result in more complete eliminationY of any chlorine or uorine that. might remain inthe graphite bars. In this regardhelium is to be preferred where graphite. is being purified for use as a neutron moderator since helium has a lowerA neutron capture cross section than nitrogen and the residual' gas remaining in thegraphite will'be less deleterious.

An alternative carrying. gas for theV chlorinating agents is anhydrous ammonia gas. and more readily available than nitrogen'. Forch'lorinatingl agents, such as chlorine, which are. gaseousiat normal temperaturesit is' not necessaryv to'use'a carryin'gagent; The p rocess ofthe invention also gaveunexpected re# sults in removing impurities heretofore not evenrsuspe'cted' Duringv the development of the process several purified and unpurilied graphite barsof` being in' theV graphite.

were tested for impurity content by subjecting them to neutron bombardmentV and determining the neutron ad'- sorption factors of thebars; It was found that the neutron adsorption of the purified'` bars was considerably less than could be accounted' f'or'bythe removal of' the known impurities.' unrecognized impurities were present in the'unpurified graphite andwere removed Vby this purification process. Radiochemical analyses finallyV revealed? that the process causedthe removal of certain rare earths present'in the impure. graphite in very minute'amounts. Some of'these rare earths have a very large neutron capture cross section.

The removal of the impurities obtained by the process of thisinvention is extremely desirable when the graphite isro be used as a4 moderator in a neutronic reactor. The' This is, offcourse, cheaper it' was* evident that" some' hitherto utilization of such highly pur'ihed graphite increases the number of neutrons available for maintainingl thechain reaction and thus increases the neutron efficiency of a reactor. This, of course; makes possible the greater overall etliciency of the reactor and also makes possible a considerable saving in the investment of ssionable material required to sustain a chain reaction.

Another advantage of the process resides in the ability to purify preshaped graphite articles without causing the erosion and disintegration thereof. Graphite bars of high density can becheaply made from' crudev petroleum coke and coal tar pitch as described in the example. By using the method of the present invention such bars can be easily purified to a very high purity Without lowering the density thereof. It is, of course, desirable to have as dense a graphite as possible when the graphite is to be used as a neutron moderator.

The process of this invention though described in its application to the purification' of graphite is not? limited thereto. The process can also be used` for puri-fyinfg ungraphitized' carbon. For example theV petroleum coke' and coal tar pitch bars, such as were graphitize'd to'form the graphite bars purified in the example could be' treated by this process. Thus it is to"beunders'toodthe foregoing inventionl is'to be takenl as illustrative rather than limiting in scope, the invention being limited onlyy as is necessitated by the prior art' and the scope of the appended' claims.

What is claimed is:

l. A process for purifyingV graphite which. comprises` the steps of subjecting the impure graphite at elevated' temperatures and up to at least 1860 C. to the actionfofV a chlorinating agent selected from the group consisting` of chlorine and fully chlorinated hydrocarbons, and sub sequently, ata temperature greater than theftemperature rangewithinfwhich carbon and uorine will react, subjecting-.the graphite tothe action of a uorinating-agentscleoted` from the group consisting offluorine, hydrogen fluoride and fully halogenatedhydrocarbons of which at least one-of the .halogens is fiuorine;

2. A process` for purifying graphite which comprises the steps-off-treatingimpure graphite with a` chlorinating. agentselected from the groupconsisting of chlorine'and fully chlorinated, hydrocarbons at elevated-temperatures and up to at least 1860" C. and subsequently.- treating-thegraphitelwith a uorinating agent selected from the group consistingof` uorine, hydrogen fluorideV and fully halogenatedhydrocarbons of Which-at least oneofthe halogens is uoriue ata temperature greater.than'l860 C.

3. A process for purifymg graphite which comprises the steps of. slowly heating the impure graphite` to` atemperatureof about-1860 C., maintaining said impure graphiteduring saidheatingperiod man-atmosphere ofa chlorinati'ngA agent selectedY from the group consistingl of ehloriner andV fully chlorinated hydrocarbons,-replacing,.when aforesaidftemperature of 1R60" C. is attained; saidVV chlorinatingagent vvithl a -iiuorinating agent selected from the group consisting of fluorine, hydrogen fluoride andifully halogenated hydrocarbonsof-which at least'one ofthe halgens is liuorine, continuing said heating and maintaining the atmosphere of'said uorinating agentuntiithev graphite attains atemperature of greaterthau 2100-v C., discontinuing, the'heating; replacing the `uoriratig.`agnt with' a non-reactive'gas and'allowingith'e'prihed graphite" to cool.

4. The process of' claim" 3' wherein the chlorinating agentis carbon 'tetrachloride and theV fluorinating agent' is dichloro-dihoromethane.

S. The process of claim B-Wherein the chlorinatingagent is chlorine `andthe uorinatin'g agent is dichloro-diuoromethane. A

6.. The process ofA claim 3 wherein the chlorinating agent. is carbon` tetrachloride andthe uorinating. agent lis carbon-tetranoride.

7. The process of claim 3`wh`erein the chlin'ina't'in"g` agent is chlorine and the uorn'ating agent is carbon drocarbonsand subsequently subjecting the graphite'at an tetrauorideelevated temperature of at least 1860 C. to the act1on of 8 A Process for purifying graphite which comprises the a luorinating agent selected from the group consisting of steps of subjecting the impure graphite at anelevated temuorme hydrqgen uonde and fully halogenafed hyqro perature to the action of a chlorinating agent selected from 5 Carbons of which at least one of the halogens 1s uorme the class consisting of chlorine and fully chlorinated hy- No references cited. 

1. A PROCESS FOR PURIFYING GRAPHITE WHICH COMPRISES THE STEPS OF SUBJECTING THE IMPURE GRAPHITE AT ELEVATED TEMPERATURES AND UP TO AT LEAST 1860* C. TO THE ACTION OF A CHLORINATING AGENT SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND FULLY CHLORINATED HYDROCARBONS, AND SUBSEQUENTLY, AT A TEMPERATURE GREATER THAN THE TEMPERATURERANGE WITHIN WHICH CARBON AND FLUORINE WILL REACT, SUBJECTING THE GRAPHITE TO THE ACTION OF A FLUORINATING AGENT SELECTED FROM THE GROUP CONSISTING OF FLUORINE, HYDROGEN FLUORIDE AND FULLY HALOGENATED HYDROCARBONS OF WHICH AT LEAST ONE OF THE HALOGENS IS FLUORINE. 